CN109705848B - One-dimensional organic semiconductor nanocoil and preparation method and application thereof - Google Patents
One-dimensional organic semiconductor nanocoil and preparation method and application thereof Download PDFInfo
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- CN109705848B CN109705848B CN201910045231.7A CN201910045231A CN109705848B CN 109705848 B CN109705848 B CN 109705848B CN 201910045231 A CN201910045231 A CN 201910045231A CN 109705848 B CN109705848 B CN 109705848B
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Abstract
The invention provides a one-dimensional organic semiconductor nano coil with high fluorescence quantum yield and a preparation method thereof, wherein perylene imide derivative monomers containing perylene anhydride and with asymmetric amphiphilic substituent groups at two ends are designed and synthesized to be used as construction units, and the construction units are self-assembled by utilizing the solubility difference of organic solvents, so that the one-dimensional organic semiconductor nano coil with a spiral coil structure is obtained, and the one-dimensional organic semiconductor nano coil has good fluorescence quantum yield up to 24%; the one-dimensional organic semiconductor nanocoil with the chiral group provides a new idea for further detecting molecules with chirality as a fluorescence method in the future; the one-dimensional organic semiconductor nanocoil with uniform and controllable size in a micrometer scale range is prepared by applying an active self-assembly mode, and the size of the one-dimensional organic semiconductor nanocoil is controlled according to different molar ratios of the used seeds to the monomers.
Description
Technical Field
The invention belongs to an organic semiconductor nano material, and particularly relates to a one-dimensional organic semiconductor nano coil with high fluorescence quantum yield, a preparation method and application thereof.
Background
Since the discovery of carbon nanotubes, due to the fact that the radial dimension of the carbon nanotubes is in the nanometer order, quantum effects and surface effects are generated, so that the carbon nanotubes have excellent optical properties, electrical properties and stable thermodynamic and mechanical properties, and have been widely paid attention and researched.
The organic semiconductor nano material has the advantages that the carbon nano material does not have, for example, the structure of the organic semiconductor nano material can be regulated and controlled, the organic semiconductor nano material can be prepared by a flexible synthesis method, the manufacturing cost of the material is low, the large-area processing is easy, the organic semiconductor nano material can be applied to a flexible substrate, the specific surface area is larger, the gas sensing device is designed with more direct advantages, and the like. Therefore, although organic semiconductor nanomaterials are starting to move relatively late compared to inorganic nanomaterials, they have developed rapidly in recent years. The one-dimensional organic semiconductor nano material prepared by taking pi conjugated organic molecules as a construction unit can be used as an effective fluorescent or conductive sensor material to realize high-sensitivity and high-selectivity detection of toxic and harmful substances.
The one-dimensional organic semiconductor nano coil belongs to a novel nano coil, and has three remarkable characteristics compared with a carbon nano tube: 1. the preparation method is different from the traditional carbon nano coil, and is obtained by self-assembling organic small molecules in a solution through the interaction between pi and pi, chiral acting force and steric hindrance through ingenious molecular design; 2. the pi-pi stacking direction of the organic semiconductor nanocoil formed by pi-pi stacking self-assembly is parallel to the long axis direction of the nanocoil, and the pi-pi stacking direction of the carbon nanocoil is vertical to the long axis direction of the nanocoil; 3. the method for assembling the supermolecule nano coil from bottom to top by the small organic molecules is more flexible and controllable, and the aim of obtaining supermolecules with different structures can be achieved by changing the molecular structure of the small organic molecules or the assembling conditions. The development of one-dimensional organic semiconductor nanocoils with high fluorescence quantum yield through molecular design is the current direction of hot research.
Disclosure of Invention
In order to solve the technical problems, the invention provides a one-dimensional organic semiconductor nanocoil, which is obtained by self-assembling a plurality of perylene imide derivatives shown as a formula (I):
wherein R is1Is a linear or branched long-chain aliphatic radical, R2Is substituted by more than one substituent group RsSubstituted aryl or arylalkylene.
According to an embodiment of the invention, R1Is straight-chain or branched C1～20An aliphatic hydrocarbon group.
According to an embodiment of the invention, RsCan be independently selected from C1～20Aliphatic hydrocarbyl-O-, C1～20Aliphatic hydrocarbyl-S-, preferably, said RsMay optionally have a chiral center; more preferably, R issIndependently selected from C1～10alkyl-O-, for example, (R) - (-) -2-butyl-O-, (S) - (+) -2-butyl-O-, (R) - (-) -2-pentyl-O, (S) - (+) -2-pentyl-O-, (S) - (-) -2-methyl-1-butyl-O-, (R) -2-methylbutyl-O-, more preferably (R) - (-) -2-butyl-O-or (S) - (+) -2-butyl-O-;
according to an embodiment of the invention, the aryl or arylalkylene group may be substituted with two RsOptionally, the aryl or arylalkylene group may be substituted with two R's having chiral centerssAnd (4) substituting.
According to an embodiment of the invention, R2Is substituted by more than one substituent group RsSubstituted C6～14Aryl or C6～14aryl-C1～10An alkylene group.
According to embodiments of the present invention, the self-assembly may be achieved through pi-pi interactions between building blocks, chiral forces, and steric hindrance.
Preferably, R1Selected from:
preferably, R2Selected from:
r is as defined above1、R2One end of the group labeled · is attached to the N atom.
According to the present invention, preferred compounds of formula (I) include:
and the pi-pi accumulation direction of the pi-pi interaction between the construction units is parallel to the long axis direction of the nanocoil.
The one-dimensional organic semiconductor nano coil is a spiral coil structure, the length of the one-dimensional organic semiconductor nano coil is 20-100 micrometers, the diameter of the one-dimensional organic semiconductor nano coil is 15-30 nanometers, and the thread pitch of the one-dimensional organic semiconductor nano coil is 150-200 nanometers.
The invention also provides a preparation method of the one-dimensional organic semiconductor nanocoil, which comprises the following steps: synthesizing a perylene bisimide derivative shown as a formula (I) as a construction unit; and then self-assembling the one-dimensional organic semiconductor nanocoil through pi-pi interaction between perylene anhydrides contained in the building units in a mixed solution of a good solvent and a poor solvent.
According to an embodiment of the present invention, the method for preparing the one-dimensional organic semiconductor nanocoil comprises the following steps:
(1) preparation R2-NH2；
(2) Dissolving perylene-3, 4,9, 10-tetracarboxylic dianhydride in an organic solvent, reacting with R1-NH2Reacting to obtain the compound of formula (II)
(3) Reacting the compound of formula (II) obtained in step (2) with R obtained in step (1)2-NH2Reacting to obtain the perylene bisimide derivative shown in the formula (I);
(4) and (4) dissolving the compound of the formula (I) obtained in the step (3) in a good solvent, adding a poor solvent, stirring, standing, and carrying out self-assembly to obtain the one-dimensional organic semiconductor nanocoil.
Wherein R is1-NH2、R2-NH2And in the compound of formula (II), R1、R2Is as defined for compounds of formula (I).
According to an embodiment of the invention, R in step (1)2-NH2The preparation method comprises the following steps:
(1a) r is to bes-H reacts with an activating reagent, a catalyst, a base to obtain a first product;
(1b) reacting the first product obtained in step (1a) with an aryl cyanide or aryl alkylene cyanide having a phenolic hydroxyl group to obtain a second product R2-CN；
(1c) The second product R obtained in the step (1b)2Reduction of-CN to obtain a third product R2-NH2。
Wherein R issR in-HsAs defined in formula (I).
According to an embodiment of the invention, R is as described in step (1a)s-H is preferably C1～10The alkyl alcohol is more preferably (R) - (-) -2-butanol, (S) - (+) -2-butanol, (R) - (-) -2-pentanol, (S) - (+) -2-pentanol, (S) - (-) -2-methyl alcohol-1-butanol, (R) -2-methylbutanol, any one or combination thereof, more preferably (R) - (-) -2-butanol or (S) - (+) -2-butanol;
r in step (1a)sThe molar ratio of the H to the activating reagent, the catalyst and the alkaline reagent is (1-20): 1: (1-40), and preferably 10:10:1: 20;
the activating reagent is preferably any one or the combination of 4-methylbenzenesulfonyl chloride, methylsulfonyl chloride, triphenylchloromethane and trifluoromethanesulfonyl chloride;
the catalyst is preferably any one of 4-dimethylaminopyridine, pyridine or a combination thereof;
the alkaline reagent is preferably any one or the combination of triethylamine, N-diisopropylethylamine, N-methylmorpholine, sodium carbonate and potassium carbonate;
the reaction temperature in the step (1a) is room temperature, and the reaction time is 8-16 hours, such as 12 hours.
According to an embodiment of the present invention, in the aryl cyanide or arylalkylene cyanide having a phenolic hydroxyl group in step (1b), the aryl group and the arylalkylene group are as defined for R in the compound of formula (I)2The aryl or arylalkylene group of (1), wherein the aryl cyanide or arylalkylene cyanide having a phenolic hydroxyl group is preferably any one or a combination of 2, 6-dihydroxybenzonitrile, 2, 5-dihydroxybenzonitrile, 2, 4-dihydroxybenzonitrile, 2, 3-dihydroxybenzonitrile, 3, 4-dihydroxybenzonitrile, 3, 5-dihydroxybenzonitrile;
the reaction in the step (1b) is carried out under the action of alkali, wherein the alkali is any one or combination of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium bicarbonate and potassium bicarbonate;
the molar ratio of the first product to the aryl cyanide or aryl alkylene cyanide having a phenolic hydroxyl group and the base is (1-10): 1, preferably (1-5): 1, and more preferably (1-3): 1-2): 1.
The reaction in the step (1b) is carried out under the anaerobic condition; the reaction temperature is 80 ℃ to 120 ℃, for example, 100 ℃; the reaction time is 8 to 16 hours, for example 12 hours.
According to an embodiment of the present invention, the reduction of step (1c) may be performed under the action of a hydride reducing agent, such as lithium aluminum hydride, sodium borohydride, borane, sodium cyanoborohydride;
r obtained in the step (1b)2The molar ratio of-CN to hydride is 1 (1-10), preferably 1 (1-5), and further optimized to be 1 (2-3);
the reaction in the step (1c) is carried out under the anaerobic condition; the reaction time is 8 to 16 hours, for example 12 hours.
According to an embodiment of the present invention, the perylene-3, 4,9, 10-tetracarboxylic dianhydride and the R in step (2) are reacted with1-NH2The molar ratio of (a) is 1 (1 to 50), preferably 1 (1 to 30), more preferably 1 (5 to 20), and for example, may be 1: 10.6;
the organic solvent is imidazole, and the using amount of the imidazole is 8-20 g, for example 10g, of perylene-3, 4,9, 10-tetracarboxylic dianhydride per 100 mg;
the reaction temperature is 100-150 ℃, for example, 110-130 ℃; the reaction time is 8-16 hours, such as 12 hours;
according to the embodiment of the invention, the specific reaction process of the step (2) is as follows: mixing perylene-3, 4,9, 10-tetracarboxylic dianhydride and imidazole, heating to 110-130 ℃ for dissolution, and injecting R into the mixed solution1-NH2And (3) reacting to obtain a reaction solution, adding 8-15 ml of ethanol and 8-15 ml of concentrated hydrochloric acid into the reaction solution, stirring overnight, taking out a product, washing with water until the pH value is neutral, and drying for later use.
According to an embodiment of the invention, the compound of formula (II) in step (3) is reacted with R obtained in step (1)2-NH2The molar ratio of (A) to (B) is 1 (1-10), preferably 1 (1.5-6);
the reaction temperature is 100-150 ℃, for example, 110-130 ℃; the reaction time is 1-7 hours, preferably 3-5 hours;
the reaction is preferably carried out in an organic solvent, preferably imidazole.
According to an embodiment of the invention, the solvent is used in an amount of 1 to 2g, for example 1.4g, per 10mg of compound of formula (II).
According to the embodiment of the invention, after the reaction in the step (3) is finished, concentrated hydrochloric acid is added and stirred to obtain the compound of the formula (I);
the addition amount of the concentrated hydrochloric acid is 2-5 mL, such as 4mL, relative to 10mg of the compound of the formula (II);
the mass fraction of the concentrated hydrochloric acid is 36-38%;
the time for stirring after adding the concentrated hydrochloric acid is 8-20 hours, such as 12 hours.
According to an embodiment of the present invention, the volume ratio of the good solvent to the poor solvent in the step (4) is 1:5 to 1: 20;
the good solvent is selected from dichloromethane, chloroform, o-dichlorobenzene and 1, 2-dichloroethane;
the poor solvent is selected from methanol, ethanol, cyclohexane, isopropanol and phenethyl alcohol;
the standing time is 0.5-10 days, and preferably 7 days.
According to the embodiment of the invention, the poor solvent is added in the step (4), then the mixture is stirred and stood to obtain suspension containing the one-dimensional organic semiconductor nanocoil, the suspension is stood, the prepared one-dimensional organic semiconductor nanocoil at the bottom of the container is taken out, the suspension is placed in the poor solvent, shaken uniformly and dispersed and washed repeatedly to obtain the one-dimensional organic semiconductor nanocoil;
the poor solvent and the standing time are defined as above.
Further, the invention also provides a preparation method of the dimension-controllable one-dimensional organic semiconductor nanocoil, which comprises the following steps:
1) preparing the one-dimensional organic semiconductor nanocoil with a certain size as a seed;
2) dissolving the compound of formula (I) as a monomer in a good solvent, adding a poor solvent, adding the seeds obtained in the step 1), and performing active self-assembly to obtain the size-controllable one-dimensional organic semiconductor nanocoil.
According to an embodiment of the present invention, the method for preparing the seed in step 1) comprises the steps of:
1a) preparing the one-dimensional organic semiconductor nanocoil;
1b) and carrying out ultrasonic treatment on the one-dimensional organic semiconductor nanocoil at a certain temperature to obtain the seeds with a certain size.
According to an embodiment of the present invention, the one-dimensional organic semiconductor nanocoil in step 1a) may be obtained by the method of steps (1) to (4) described above;
according to an embodiment of the invention, the certain temperature in step 1b) is between-80 ℃ and-30 ℃, preferably between-70 ℃ and-50 ℃, and may be, for example, -50 ℃, -60 ℃, -70 ℃;
according to the embodiment of the invention, the ultrasonic wave in the step 1b) has a power of 30-100W, for example, 50W; the ultrasonic treatment time is 0.1-3 hours, preferably 0.5-2 hours;
according to an embodiment of the present invention, the size of the seeds in step 1b) is 0.3 to 1.5 microns, preferably 0.5 to 1 micron;
the seed is in a spiral coil structure.
According to an embodiment of the present invention, the good solvent in step 2) is selected from dichloromethane, chloroform, o-dichlorobenzene, 1, 2-dichloroethane;
the poor solvent is selected from methanol, ethanol, cyclohexane, isopropanol and phenethyl alcohol;
according to an embodiment of the present invention, the molar ratio of the seeds to the monomers in step 2) is 1 (1 to 20), preferably 1 (1 to 10), and may be, for example, 1:1,1:2,1:5,1: 10;
the molar ratio of the seed to the monomer determines the size of the resulting size-controllable one-dimensional organic semiconductor nanocoil.
According to the embodiment of the invention, as the molar ratio of the seeds to the monomers is reduced, the length of the obtained one-dimensional organic semiconductor nanocoil is increased proportionally: when the molar ratio of the seeds to the monomers is 1:1, the length of the one-dimensional organic semiconductor nanocoil with controllable size is 1.2-2.0 micrometers; when the molar ratio is 1:5, the length of the one-dimensional organic semiconductor nanocoil with controllable size is 3.6-4.8 micrometers; when the molar ratio is 1:10, the length of the one-dimensional organic semiconductor nanocoil with controllable size is 8-11 micrometers.
According to the embodiment of the invention, the poor solvent is added in the step 2), and then the mixture is stirred and placed still, so that suspension containing the one-dimensional organic semiconductor nanocoil with controllable size is obtained, the suspension is placed still, the one-dimensional organic semiconductor nanocoil with controllable size prepared at the bottom of the container is taken out, and the suspension is placed in the poor solvent, shaken uniformly and dispersed and washed repeatedly, so that the one-dimensional organic semiconductor nanocoil with controllable size is obtained.
Wherein the poor solvent has the above-mentioned definition.
According to the embodiment of the present invention, the standing time after the addition of the poor solvent is 6 to 24 hours, for example, 12 hours;
the standing time of the suspension is 0.5-10 days, and preferably 7 days.
The invention also provides a porous film formed by the one-dimensional organic semiconductor nanocoil.
According to an embodiment of the present invention, the porous film is formed by coating the one-dimensional organic semiconductor nanocoil dispersed in a poor solvent; the poor solvent is methanol, ethanol, cyclohexane, isopropanol or phenethyl alcohol; the coating film may be applied to a solid substrate, such as a polytetrafluoroethylene film.
The porous membrane is a network structure having a fluorescence quantum yield of up to 24%.
The invention also provides application of the one-dimensional organic semiconductor nanocoil in fluorescence detection.
According to an embodiment of the present invention, when formula (I) in the one-dimensional organic semiconductor nanocoil has a chiral center, the application further comprises detecting the chiral molecule according to the force of its chiral site to have a chiral recognition effect on the chiral molecule.
Further, the present invention also provides a fluorescence detector comprising the one-dimensional organic semiconductor nanocoil or the porous membrane.
The invention has the beneficial effects that:
1. the invention provides a one-dimensional organic semiconductor nanocoil with high fluorescence quantum yield and a preparation method thereof.A perylene imide derivative monomer containing perylene anhydride and provided with asymmetric amphipathic substituent groups at two ends is designed and synthesized to be used as a construction unit, and self-assembly is carried out by utilizing the difference of organic solvent solubility, so that the one-dimensional organic semiconductor nanocoil with a spiral coil structure is obtained, the fluorescence is red-shifted relative to the construction unit monomer, and the arrangement mode of aggregates is J-shaped molecular arrangement; the one-dimensional organic semiconductor nanocoil has good fluorescence quantum yield (up to 24%); the one-dimensional organic semiconductor nanocoil with the chiral group provides a new idea for further detecting molecules with chirality as a fluorescence method in the future;
2. the invention provides a preparation method of a one-dimensional organic semiconductor nanocoil with controllable size, which can prepare the one-dimensional organic semiconductor nanocoil with uniform and controllable size in a micrometer scale range in an active self-assembly mode, and realize the control of the size of the one-dimensional organic semiconductor nanocoil according to different molar ratios of used seeds and monomers;
3. the one-dimensional organic semiconductor nanocoil provided by the invention can form a porous membrane with high fluorescence quantum yield, and the one-dimensional organic semiconductor nanocoil or the porous membrane can be applied as a fluorescent sensor material.
Drawings
FIG. 1 shows the mass spectrum data of perylene imide derivative monomer containing perylene anhydride with one end of (2R,6R) -di-sec-butoxybenzyl and the other end of dodecyl chain substituted in example 1 of the invention, and the relative molecular mass is 792.6.
FIG. 2 shows the perylene imide derivative monomer containing perylene anhydride with one end of (2R,6R) -di-sec-butoxybenzyl and the other end of dodecyl chain substituted in example 1 of the present invention1H-NMR spectrum.
FIG. 3 is a mass spectrum of the perylene imide derivative monomer containing perylene anhydride with one end of (2S,6S) -di-sec-butoxybenzyl and the other end of dodecyl chain substituted according to example 2 of the present invention, and the relative molecular mass is 792.6.
FIG. 4 shows perylene imide derivative monomers containing perylene anhydride substituted with (2S,6S) -di-sec-butoxybenzyl group at one end and dodecyl chain at the other end in example 2 of the present invention1H-NMR spectrum.
FIG. 5 is an ultraviolet absorption spectrum of the monomer and one-dimensional organic semiconductor nanocoil prepared in example 2 of the present invention.
FIG. 6 is a graph of UV-VIS absorption spectra of one-dimensional organic semiconductor nanocoils of different chiralities according to examples 1 and 2 of the present invention.
FIG. 7 shows fluorescence emission spectra of the monomer and one-dimensional organic semiconductor nanocoil prepared in example 2 of the present invention.
FIG. 8 is a CD spectrum of the suspension of the one-dimensional organic semiconductor nanocoil with different chiralities in the examples 1 and 2 of the present invention.
FIG. 9 is a scanning electron micrograph of the one-dimensional organic semiconductor nanocoil prepared in example 1 of the present invention. Fig. 9a is a large-area one-dimensional organic semiconductor nanocoil, and fig. 9b is an enlarged view of the one-dimensional organic semiconductor nanocoil.
FIG. 10 is a transmission electron micrograph of a one-dimensional organic semiconductor nanocoil prepared in example 1 of the present invention. Fig. 10a is a large-area one-dimensional organic semiconductor nanocoil, and fig. 10b is an enlarged view of the one-dimensional organic semiconductor nanocoil.
FIG. 11 is an atomic force microscope photograph of the one-dimensional organic semiconductor nanocoil prepared in example 1 of the present invention. Fig. 11a is a large-area one-dimensional organic semiconductor nanocoil, and fig. 11b is an enlarged view of the one-dimensional organic semiconductor nanocoil.
Fig. 12 is a scanning electron micrograph of the structures of the one-dimensional organic semiconductor nanocoils prepared in example 1 of the present invention obtained by active self-assembly, fig. 12a to 12c are seed structures of the one-dimensional organic semiconductor nanocoils with different lengths, fig. 12d to 12f are structures of the one-dimensional organic semiconductor nanocoils obtained by active self-assembly when the molar ratio of the seeds to the monomers is 1:1, fig. 12g to 12i are structures of the one-dimensional organic semiconductor nanocoils obtained by active self-assembly when the molar ratio of the seeds to the monomers is 1:5, and fig. 12j to 12l are structures of the one-dimensional organic semiconductor nanocoils obtained by active self-assembly when the molar ratio of the seeds to the monomers is 1:10.
FIG. 13 is a scanning electron micrograph of a one-dimensional organic semiconductor nanocoil prepared in example 2 of the present invention. Fig. 13a is a large-area one-dimensional organic semiconductor nanocoil, and fig. 13b is an enlarged view of the one-dimensional organic semiconductor nanocoil.
FIG. 14 is a transmission electron micrograph of the one-dimensional organic semiconductor nanocoil prepared in example 2 of the present invention. Fig. 14a is a large-area one-dimensional organic semiconductor nanocoil, and fig. 14b is an enlarged view of the one-dimensional organic semiconductor nanocoil.
FIG. 15 is an atomic force microscope photograph of the one-dimensional organic semiconductor nanocoil prepared in example 2 of the present invention. Fig. 15a is a large-area one-dimensional organic semiconductor nanocoil, and fig. 15b is an enlarged view of the one-dimensional organic semiconductor nanocoil.
Fig. 16 is a scanning electron microscope photograph of the one-dimensional organic semiconductor nanocoil prepared in example 2 of the present invention, in which structures of the one-dimensional organic semiconductor nanocoil with different lengths are obtained by using an active self-assembly method, 16a to 16c are one-dimensional coil seed structures required by the active self-assembly, 16d to 16f are one-dimensional coil structures obtained by the active self-assembly when a molar ratio of seeds to monomers is 1:1, 16g to 16i are one-dimensional coil structures obtained by the active self-assembly when a molar ratio of seeds to monomers is 1:5, and 16j to 16l are one-dimensional coil structures obtained by the active self-assembly when a molar ratio of seeds to monomers is 1:10.
Definition and description of terms
Unless otherwise indicated, the definitions of radicals and terms recited in the specification and claims, including their definitions as examples, exemplary definitions, preferred definitions, definitions of specific compounds in the examples, and the like, may be combined with each other in any combination and association. The definitions of the groups and the structures of the compounds in such combinations and after the combination are within the scope of the present specification.
The term "aliphatic hydrocarbon group" is understood to preferably mean a saturated or unsaturated, linear or branched, chain hydrocarbon group, the type of which may be selected from alkyl, alkenyl, alkynyl and the like, the number of carbon atoms of which is generally from 1 to 20, further preferred ranges include from 1 to 13, from 2 to 8, from 3 to 7, from 4 to 6 and the like, and may include in particular, but not limited to, the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 1-ethylethenyl, 1-methyl-2-propenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 1-methyl-2-propynyl, 3-butynyl, 1-pentynyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 2-propenyl, 2-butenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-, 2-pentynyl, 2-hexynyl, 3-hexynyl and 1-hexynyl; the "aliphatic radical" moiety contained in the other radicals (e.g. aliphatic radical-O-) is as explained above.
The term "aryl" is understood to mean preferably a mono-, bi-or tricyclic hydrocarbon ring having a monovalent aromatic or partially aromatic character of 6 to 20 carbon atoms. The term "C6-14Aryl "is understood to mean a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partial aromaticity of 6, 7, 8, 9,10, 11, 12, 13 or 14 carbon atoms (" C)6-14Aryl group "), in particular a ring having 6 carbon atoms (" C6Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C9Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C10Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C13Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C)14Aryl), such as anthracenyl.
The term "alkylene" is understood to mean preferably a straight-chain or branched saturated hydrocarbon group having 1 to 20 carbon atoms, more preferably, C1-10Alkylene, i.e. straight-chain or branched saturated hydrocarbon radicals having 1,2, 3,4, 5, 6, 7, 8, 9 or 10 carbon atoms. In particular, the radicals have 1,2, 3,4 carbon atoms ("C)1-4Alkylene) such as methylene, ethylene, propylene, butylene。
The term "alkyl" is used in the case where one end of the above-mentioned "alkylene" structure is H.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The preparation method comprises the steps of preparing a perylene bisimide derivative monomer which has the following molecular formula, wherein one end of the perylene bisimide derivative monomer is (2R,6R) -di-sec-butoxybenzyl, the other end of the perylene bisimide derivative monomer is substituted by dodecyl chain and contains perylene anhydride, and preparing the one-dimensional organic semiconductor nanocoil by using the perylene bisimide derivative monomer as a construction unit.
(1) Preparation of (2R,6R) -di-sec-butoxybenzylamine
a. After 5 g of (R) - (-) -2-butanol was dissolved in 100 ml of dichloromethane, the solution was added dropwise to a dichloromethane solution containing 4-methylbenzenesulfonyl chloride, 4-dimethylaminopyridine and triethylamine to obtain a mixed solution, wherein the ratio of (R) - (-) -2-butanol: 4-methylbenzenesulfonyl chloride: 4-dimethylaminopyridine: the molar ratio of triethylamine is 10:10:1: 20; stirring the mixed solution at room temperature for about 12 hours, after the reaction is finished, washing the obtained mixture with saturated sodium bicarbonate aqueous solution and water respectively, and then extracting an organic phase by using dichloromethane; drying the extracted organic phase with anhydrous sodium sulfate, and further purifying with column chromatography (silica gel column chromatography with n-hexane/ethyl acetate as eluent (n-hexane: ethyl acetate volume ratio of 20: 1)) to obtain a first product;
b. adding 600 mg of 2, 6-dihydroxybenzonitrile into 30 ml of N, N-dimethylformamide solution containing 2.25 g of the first product and 0.5 g of potassium carbonate, and stirring for 12 hours at 100 ℃ under oxygen-free conditions to carry out reaction; after the reaction is finished, adding 20 ml of water into the obtained reaction liquid, stirring, adding 30 ml of ethyl acetate into the mixed solution, extracting for three times, drying the obtained organic phase, and further purifying by using a column chromatography method to obtain a second product (2R,6R) -di-sec-butoxy benzonitrile;
c. dissolving 90 mg of lithium aluminum hydride in 20 ml of tetrahydrofuran, cooling to 0 ℃ in an ice water bath, slowly dropwise adding 250 mg of the second product obtained in the step (2) in 4ml of tetrahydrofuran into the tetrahydrofuran in which the lithium aluminum hydride is dissolved, stirring under anaerobic conditions, heating, condensing and refluxing for 12 hours. After the reaction is finished, 0.1 ml of water, 0.2 ml of a 15% sodium hydroxide aqueous solution and 0.3 ml of water are sequentially added into the obtained reaction solution, an organic solvent is removed through rotary evaporation, 40 ml of water is added into the residual substance, extraction is carried out for three times by using 60 ml of ethyl acetate, the obtained organic phase is dried and further purified by column chromatography, and a third product (2R,6R) -di-sec-butoxybenzylamine is obtained.
(2) Mixing 70 mg of perylene-3, 4,9, 10-tetracarboxylic dianhydride and 7 g of imidazole at room temperature, heating the mixture to 120 ℃ to dissolve the perylene-3, 4,9, 10-tetracarboxylic dianhydride and the imidazole, injecting 350 mg of dodecylamine solution into the mixed solution to react to obtain reaction liquid, adding 10 ml of ethanol and 10 ml of concentrated hydrochloric acid (the mass percentage is 36% -38%) into the reaction liquid, and stirring the mixture overnight; taking out the product, washing with water until the pH value is neutral, and drying;
(3) taking 50 mg of the product obtained after drying in the step (2), 7 g of imidazole and 80 mg of (2R,6R) -di-sec-butoxybenzylamine were added thereto; under the protection of inert gas, reacting for 4 hours at 120 ℃ to obtain reaction liquid, then adding 20 ml of concentrated hydrochloric acid (the mass percent is 36-38%) into the reaction liquid, stirring overnight, and taking out the product to obtain the perylene bisimide derivative containing perylene anhydride and having asymmetric amphiphilic substituent groups at two ends.
The mass spectrum data spectrogram is shown in FIG. 1，1The H-NMR spectrum is shown in FIG. 2.
(4) And (3) dissolving the perylene bisimide derivative monomer containing perylene anhydride and having asymmetric amphipathic substituent groups at two ends, obtained in the step (3), in 50 ml or 100 ml of chloroform, taking out 5ml of solution after the perylene bisimide derivative monomer is completely dissolved, adding the solution into 25 ml, 40 ml or 100 ml of ethanol, rapidly stirring, standing for 7 days, and self-assembling the perylene bisimide derivative containing perylene anhydride and having asymmetric amphipathic substituent groups at two ends through pi-pi interaction between the perylene bisimides to obtain a suspension containing a plurality of one-dimensional organic semiconductor nanocoils with high fluorescence quantum yield, wherein the pi-pi stacking direction is parallel to the long axis direction of the nanocoils.
And standing the obtained suspension containing the plurality of one-dimensional organic semiconductor nanocoils with high fluorescence quantum yield for 7 days, taking out the one-dimensional organic semiconductor nanocoils with high fluorescence quantum yield prepared at the bottom of the container, placing the one-dimensional organic semiconductor nanocoils in ethanol, shaking up, dispersing and repeatedly washing to obtain the one-dimensional organic semiconductor nanocoils with high fluorescence quantum yield.
(5) And (3) carrying out ultrasonic treatment on the one-dimensional organic semiconductor nano coil obtained in the step (4) for 1 hour at the temperature of-50 ℃ and under the power intensity of 50W to obtain a spiral coil structure with the size of 0.5-1 micron as a seed required by active self-assembly.
(6) Dissolving the perylene imide derivative monomer containing perylene anhydride and having asymmetric amphipathic substituent groups at two ends obtained in the step (3) in 50 ml of dichloromethane, taking out three parts after the perylene imide derivative monomer is completely dissolved, adding 5ml of solution into 25 ml of methanol respectively, and then respectively adding the solution into the methanol according to the seed ratio: and (3) adding the seeds obtained in the step (5) into the mixture according to the monomer molar ratio of 1:1,1: 5 and 1:10, rapidly stirring the mixture, standing the mixture for 12 hours, and obtaining suspension liquid with three parts of different scale ranges and each part containing a plurality of one-dimensional organic semiconductor nanocoils with uniform sizes in an active self-assembly mode.
(7) And (4) standing the three suspensions obtained in the step (6) for 7 days, respectively taking out the one-dimensional organic semiconductor nano-coils with uniform size prepared at the bottom of the container, placing the organic semiconductor nano-coils in a poor solvent, shaking up, dispersing and repeatedly washing to obtain the one-dimensional organic semiconductor nano-coils with the sizes corresponding to the sizes of the organic semiconductor nano-coils.
Example 2
The preparation method comprises the steps of preparing a perylene bisimide derivative monomer which has the following molecular formula, wherein one end of the perylene bisimide derivative monomer is (2S,6S) -di-sec-butoxybenzyl, and the other end of the perylene bisimide derivative monomer is substituted by a dodecyl chain and contains perylene anhydride, and preparing the one-dimensional organic semiconductor nanocoil by using the perylene bisimide derivative monomer as a building unit.
(1) Preparation of (2S,6S) -di-sec-butoxybenzylamine
a. After 5 g of (S) - (-) -2-butanol was dissolved in 100 ml of dichloromethane, the solution was added dropwise to a dichloromethane solution containing 4-methylbenzenesulfonyl chloride, 4-dimethylaminopyridine and triethylamine to obtain a mixed solution, wherein the ratio of (S) - (-) -2-butanol: 4-methylbenzenesulfonyl chloride: 4-dimethylaminopyridine: the molar ratio of triethylamine is 10:10:1: 20; stirring the mixed solution at room temperature for about 12 hours, after the reaction is finished, washing the obtained mixture with saturated sodium bicarbonate aqueous solution and water respectively, and then extracting an organic phase by using dichloromethane; drying the extracted organic phase with anhydrous sodium sulfate, and further purifying with column chromatography (silica gel column chromatography with n-hexane/ethyl acetate as eluent (n-hexane: ethyl acetate volume ratio of 20: 1)) to obtain a first product;
b. adding 600 mg of 2, 6-dihydroxybenzonitrile into 30 ml of N, N-dimethylformamide solution containing 2.25 g of the first product and 0.5 g of potassium carbonate, and stirring for 12 hours at 100 ℃ under oxygen-free conditions to carry out reaction; after the reaction is finished, adding 20 ml of water into the obtained reaction liquid, stirring, adding 30 ml of ethyl acetate into the mixed solution, extracting for three times, drying the obtained organic phase, and further purifying by using a column chromatography method to obtain a second product (2S,6S) -di-sec-butoxy benzonitrile;
c. dissolving 90 mg of lithium aluminum hydride in 20 ml of tetrahydrofuran, cooling to 0 ℃ in an ice water bath, slowly dropwise adding 250 mg of the second product obtained in the step (2) in 4ml of tetrahydrofuran into the tetrahydrofuran in which the lithium aluminum hydride is dissolved, stirring under anaerobic conditions, heating, condensing and refluxing for 12 hours. After the reaction is finished, 0.1 ml of water, 0.2 ml of a 15% sodium hydroxide aqueous solution and 0.3 ml of water are sequentially added into the obtained reaction solution, an organic solvent is removed through rotary evaporation, 40 ml of water is added into the residual substance, extraction is carried out for three times by using 60 ml of ethyl acetate, the obtained organic phase is dried and further purified by column chromatography, and a third product (2S,6S) -di-sec-butoxybenzylamine is obtained.
(2) Mixing 70 mg of perylene-3, 4,9, 10-tetracarboxylic dianhydride and 7 g of imidazole at room temperature, heating the mixture to 110-130 ℃ for dissolution, injecting 350 mg of dodecylamine solution into the mixed solution for reaction to obtain reaction solution, adding 10 ml of ethanol and 8-15 ml of concentrated hydrochloric acid (the mass fraction is 36-38%) into the reaction solution, and stirring the mixture overnight; taking out the product, washing with water until the pH value is neutral, and drying;
(3) taking 50 mg of the product obtained after drying in the step (2), and adding 7 g of imidazole and 70 mg of (R) -2, 6-diisobutylbenzylamine; under the protection of inert gas, reacting for 4 hours at 120 ℃ to obtain reaction liquid, then adding 20 ml of concentrated hydrochloric acid (the mass percent is 36-38%) into the reaction liquid, stirring overnight, and taking out the product to obtain the perylene bisimide derivative containing perylene anhydride and having asymmetric amphiphilic substituent groups at two ends.
The mass spectrum data spectrum is shown in figure 3,1the H-NMR spectrum is shown in FIG. 4.
(4) And (3) dissolving the perylene bisimide derivative monomer containing perylene anhydride and having asymmetric amphipathic substituent groups at two ends, obtained in the step (3), in 50 ml or 100 ml of chloroform, taking out 5ml of solution after the perylene bisimide derivative monomer is completely dissolved, adding the solution into 25 ml, 40 ml or 100 ml of ethanol, rapidly stirring, standing for 7 days, and self-assembling the perylene bisimide derivative containing perylene anhydride and having asymmetric amphipathic substituent groups at two ends through pi-pi interaction between the perylene bisimides to obtain a suspension containing a plurality of one-dimensional organic semiconductor nanocoils with high fluorescence quantum yield, wherein the pi-pi stacking direction is parallel to the long axis direction of the nanocoils.
And standing the obtained suspension containing the plurality of one-dimensional organic semiconductor nanocoils with high fluorescence quantum yield for 7 days, taking out the one-dimensional organic semiconductor nanocoils with high fluorescence quantum yield prepared at the bottom of the container, placing the one-dimensional organic semiconductor nanocoils in ethanol, shaking up, dispersing and repeatedly washing to obtain the one-dimensional organic semiconductor nanocoils with high fluorescence quantum yield.
(5) And (3) carrying out ultrasonic treatment on the one-dimensional organic semiconductor nano coil obtained in the step (4) for 1 hour at the temperature of-50 ℃ and under the power intensity of 50W to obtain a spiral coil structure with the size of 0.5-1 micron as a seed required by active self-assembly.
(6) Dissolving the perylene imide derivative monomer containing perylene anhydride and having asymmetric amphipathic substituent groups at two ends obtained in the step (3) in 50 ml of dichloromethane, taking out three parts after the perylene imide derivative monomer is completely dissolved, adding 5ml of solution into 25 ml of methanol respectively, and then respectively adding the solution into the methanol according to the seed ratio: and (3) adding the seeds obtained in the step (5) into the mixture according to the monomer molar ratio of 1:1,1: 5 and 1:10, rapidly stirring the mixture, standing the mixture for 12 hours, and obtaining suspension liquid with three parts of different scale ranges and each part containing a plurality of one-dimensional organic semiconductor nanocoils with uniform sizes in an active self-assembly mode.
(7) And (4) standing the three suspensions obtained in the step (6) for 7 days, respectively taking out the one-dimensional organic semiconductor nano-coils with uniform size prepared at the bottom of the container, placing the organic semiconductor nano-coils in a poor solvent, shaking up, dispersing and repeatedly washing to obtain the one-dimensional organic semiconductor nano-coils with the sizes corresponding to the sizes of the organic semiconductor nano-coils.
Example 3 test example
The monomer and the one-dimensional organic semiconductor nanocoil prepared in the above examples 1 and 2 were characterized and analyzed by uv-vis absorption spectroscopy, fluorescence emission spectroscopy, circular dichroism, atomic force microscopy, scanning electron microscopy, and transmission electron microscopy, respectively.
As shown in fig. 5, the uv-vis absorption spectra of the monomer and one-dimensional organic semiconductor nanocoil prepared in example 2 show that the absorption band edge of the nanocoil is red-shifted compared to the monomer molecule.
As shown in fig. 6, the ultraviolet-visible absorption spectra of the one-dimensional organic semiconductor nanocoils prepared in example 1 and example 2 show that the absorbance of the one-dimensional organic semiconductor nanocoils of the same concentration and different chiralities are close to each other.
As shown in FIG. 7, the fluorescence emission spectrum of the monomer and one-dimensional organic semiconductor nanocoil prepared in example 2 shows that the maximum fluorescence emission wavelength of the nanocoil is 630nm, which is red-shifted by 50nm compared with the single-molecule fluorescence emission.
As shown in fig. 8, CD spectrograms of the suspensions containing the one-dimensional organic semiconductor nanocoils with different chiralities prepared in the examples 1 and 2 show that CD signals of the one-dimensional organic semiconductor nanocoils with different chiralities are obviously mirrored in a poor solvent, which indicates that the prepared one-dimensional organic semiconductor nanocoil has a single chirality.
As shown in fig. 9, which is a scanning electron micrograph of the one-dimensional organic semiconductor nanocoil prepared in example 1, it can be seen from the micrograph that the diameter of the product is less than 50nm and the length is in the micrometer range.
The transmission electron micrograph of the one-dimensional organic semiconductor nanocoil prepared in example 1 shown in fig. 10 and the atomic force microscope micrograph of the one-dimensional organic semiconductor nanocoil prepared in example 1 shown in fig. 11 show that the product is a one-dimensional helical nanocoil, a left-handed helical coil structure with a length of 20-100 microns, a diameter of 15-30 nanometers and a thread pitch of 150-200 nanometers. And (3) measuring the fluorescence quantum yield of the obtained one-dimensional organic semiconductor nanocoil, wherein the fluorescence quantum yield is up to 24%.
Fig. 12 is a scanning electron micrograph of a one-dimensional organic semiconductor nanocoil prepared by an active self-assembly method in example 1. Scanning electron microscope photographs of structures of the one-dimensional organic semiconductor nano-coil with different lengths are obtained by the one-dimensional organic semiconductor nano-coil in an active self-assembly mode, and it can be seen from the photographs that the size of a seed structure obtained by ultrasonic processing of a product is 0.5-1.2 micrometers, the length of the one-dimensional nano-coil with the ratio of 1:1 is 1.2-2.4 micrometers, the length of the one-dimensional nano-coil with the ratio of 1:5 is 3.6-4.8 micrometers, and the length of the one-dimensional nano-coil with the ratio of 1:10 is 8-11 micrometers. The length of the obtained aggregate is increased in proportion, so that the size of the one-dimensional nanocoil structure is controllable.
As shown in fig. 13, a scanning electron micrograph of the one-dimensional organic semiconductor nanocoil prepared in example 2 shows that the diameter of the product is less than 50nm and the length is in the micrometer range.
The transmission electron microscope photograph of the one-dimensional organic semiconductor nanocoil prepared in example 2 shown in fig. 14 and the atomic force microscope photograph of the one-dimensional organic semiconductor nanocoil prepared in example 2 shown in fig. 15 show that the product is a nanocoil with a one-dimensional spiral coil structure, and the right-handed spiral coil structure has a length of 20-100 microns, a diameter of 15-30 nanometers and a thread pitch of 150-200 nanometers. And (3) measuring the fluorescence quantum yield of the obtained one-dimensional organic semiconductor nanocoil, wherein the fluorescence quantum yield is up to 24%.
Fig. 16 is a scanning electron micrograph of a one-dimensional organic semiconductor nanocoil prepared by an active self-assembly method in example 2. Scanning electron microscope photographs of structures of the one-dimensional organic semiconductor nano-coil with different lengths are obtained by the one-dimensional organic semiconductor nano-coil in an active self-assembly mode, and it can be seen from the photographs that the size of a seed structure obtained by ultrasonic processing of a product is 0.6-1.0 micron, after the active self-assembly, the length of the one-dimensional nano-coil with the ratio of 1:1 is 1.2-2.0 microns, the length of the one-dimensional nano-coil with the ratio of 1:5 is 3.0-5.0 microns, and the length of the one-dimensional nano-coil with the ratio of 1:10 is 6-9 microns. The length of the obtained aggregate is increased in proportion, so that the size of the one-dimensional nanocoil structure is controllable.
Determination of fluorescence quantum yield:
the instrument used for the measurement was a Hamamatsu C11247 fluorescence quantum yield spectrometer.
The one-dimensional organic semiconductor nanocoil prepared in the above example 2 is dispersed in ethanol and then applied dropwise to a polytetrafluoroethylene film to form a porous film with a mesh structure, and the optimal excitation wavelength is selected to be 455 nm by measuring the fluorescence excitation spectrum of the sample.
The single wavelength scanning mode is selected for testing, the fluorescence quantum yield of the sample is measured under the optimal excitation wavelength of 455 nanometers, 3 membranes of each sample drop are tested in parallel, and the average value is 24%.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A one-dimensional organic semiconductor nanocoil is characterized in that the one-dimensional organic semiconductor nanocoil is obtained by self-assembling a plurality of perylene imide derivatives shown as a formula (I):
（I），
wherein R is1Selected from:
R2selected from:
r is as defined above1、R2The end of the group labeled @ is attached to the N atom.
2. The one-dimensional organic semiconductor nanocoil according to claim 1, wherein the compound of formula (I) is selected from the following structures:
3. the one-dimensional organic semiconductor nanocoil as claimed in claim 1 or 2, wherein the one-dimensional organic semiconductor nanocoil has a spiral coil structure, a length of 20-100 μm, a diameter of 15-30 nm, and a pitch of 150-200 nm.
4. A method for preparing a one-dimensional organic semiconductor nanocoil according to any one of claims 1 to 3, comprising the steps of:
(1) preparation R2-NH2；
(2) Dissolving perylene-3, 4,9, 10-tetracarboxylic dianhydride in an organic solvent, reacting with R1-NH2Reacting to obtain the compound of formula (II)
（II）；
(3) Reacting the compound of formula (II) obtained in step (2) with R obtained in step (1)2-NH2Reacting to obtain a compound shown in a formula (I);
(4) dissolving the compound of formula (I) obtained in the step (3) in a good solvent, adding a poor solvent, stirring, standing, and self-assembling to obtain the one-dimensional organic semiconductor nanocoil;
wherein R is1-NH2、R2-NH2And in the compound of formula (II), R1、R2Are as defined for compounds of formula (I);
the good solvent is selected from dichloromethane, chloroform, o-dichlorobenzene and 1, 2-dichloroethane;
the poor solvent is selected from methanol, ethanol, cyclohexane, isopropanol and phenethyl alcohol.
5. The method according to claim 4, wherein the standing time is 0.5 to 10 days.
6. A method for preparing a one-dimensional organic semiconductor nanocoil with controllable size according to any one of claims 1 to 3, comprising the steps of:
1) preparing the one-dimensional organic semiconductor nanocoil with a certain size as a seed;
2) dissolving a compound of formula (I) as a monomer in a good solvent, adding a poor solvent, adding the seeds obtained in the step 1), and performing active self-assembly to obtain the one-dimensional organic semiconductor nanocoil with controllable size;
the preparation method of the seeds in the step 1) comprises the following steps:
1a) preparing the one-dimensional organic semiconductor nanocoil;
1b) carrying out ultrasonic treatment on the one-dimensional organic semiconductor nanocoil at a certain temperature to obtain the seeds with a certain size;
the molar ratio of the seeds to the monomers in the step 2) is 1 (1-20);
the good solvent is selected from dichloromethane, chloroform, o-dichlorobenzene and 1, 2-dichloroethane;
the poor solvent is selected from methanol, ethanol, cyclohexane, isopropanol and phenethyl alcohol;
the certain temperature in the step 1b) is minus 80 ℃ to minus 30 ℃.
7. A porous film formed of the one-dimensional organic semiconductor nanocoil according to any one of claims 1 to 3, wherein the porous film is formed by coating the one-dimensional organic semiconductor nanocoil according to any one of claims 1 to 3 after being dispersed in a poor solvent; the porous membrane is a network structure having a fluorescence quantum yield of up to 24%.
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